CN102309970B - Hydro-treating catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a hydro-treating catalyst and a preparation method thereof. The catalyst comprises hydrogenation metal component, macroporous alumina and amorphous silicon aluminum; the specific surface area of the catalyst is 150 to 450m<2>/g, the pore volume is 0.3 to 0.7cm<3>/g, and the average aperture is 10 to 20 nanometers; the hydrogenation metal component is at least one of W, Mo, Ni and Co; and based on oxides, the weight content of the hydrogenation metal component in the catalyst is 35 to 70 percent. The hydro-treating catalyst has high active metal content and high pore volume and specific surface area, and is suitable for the hydro-treating process of inferior reduced pressure distillate.

Description

A kind of hydrotreating catalyst and preparation method thereof

Technical field

The present invention relates to a kind of carrier of hydrogenating catalyst and preparation method thereof, hydrotreating catalyst of a kind of especially large pore volume for the treatment of heavy distillate, bigger serface, high activity metal content and preparation method thereof.

Background technology

Along with crude quality becomes heavy, variation year by year, environmental regulation is increasingly strict, and market constantly increases the demand of clear gusoline, makes the hydrogen addition technology of producing clean fuel obtain application more and more widely.Distillate hydrogenation is processed and is referred under HTHP, and the catalytic reaction that hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation, HDM and hydrogenation of unsaturated hydrocarbons are saturated occurs on catalyst surface for feedstock oil and hydrogen.Due to crude quality variation year by year, and refinery is for increasing economic efficiency, start generally to adopt crude oil decompression deep drawing technology, make doing by original 520 ℃ of vacuum distillate bring up to more than 600 ℃, its density is increasing, boiling range is more and more higher, the molecular weight of contained hydrocarbon molecule is increasing, impurity content is also more and more, especially sulfur-bearing, the baroque condensed-nuclei aromatics compounds content of nitrogen impurity increase greatly, the difficulty of deviating from of impurity increases greatly, more easily causes that in process the carbon deposit coking reduces catalyst activity.Therefore, hydrotreated feed oil and product are all had higher requirement to hydrotreatment technology and hydrotreating catalyst, especially the hydrotreatment technology of decompressed wax oil and supporting catalyst thereof.

In catalytic field, how to prepare and there is high activity, fine selectivity and long-life effective catalyst are the problems that people pay close attention to and pay attention to always.For the catalyst with carrier loaded active component, use the carrier of high-specific surface area, can prepare the loaded catalyst of high dispersive, thereby improve the reactivity worth of catalyst; There is larger pore volume in catalyst, can improve its anti-coking or anti-Coking Behavior, and then the service life of extending catalyst, also help catalyst regeneration simultaneously.Improve pore volume and the specific area of carrier, to giving full play to the active constituent catalyst activity, improve catalyst performance, positive meaning is arranged.

Hydrotreating catalyst belongs to the supported solid porous catalyst, and its activated centre mainly concentrates on inner surface, and internal surface area accounts for more than 95% of total surface area usually.The orifice diameter of catalyst will have direct impact to reacting the process occurred with the reactant molecule magnitude relationship, and when the hydrocarbon molecule diameter of reactant is greater than the orifice diameter of catalyst, diffusion will become the control step of reaction.Along with hydrotreated feed oil becomes heavy, variation, the hydrocarbon molecule diameter increases gradually, and its structure is also more complicated, use the hydrotreating catalyst of conventional pore structure to be subject to the impact of DIFFUSION CONTROLLED more and more obvious, the hydrocarbon molecule of larger molecular weight, especially condensed-nuclei aromatics, because volume is larger, can not enter into inside, catalyst duct and be contacted with the hydrogenation sites in duct, affect the hydrodenitrogenationactivity activity of catalyst, desulphurizing activated and aromatic saturation performance.How research improves the pore structure of hydrotreating catalyst, improves pore volume and the orifice diameter of hydrotreating catalyst, and the effective ratio area that simultaneously keeps higher hydrogenation activity to distribute, be a problem that has very much realistic meaning.

Carrier of hydrogenating catalyst pore volume prepared by conventional method is generally at 0.7mL/g～1.3mL/g, and aperture is generally at 5～12nm, and surface area is generally at 250m ²/ g～600m ²/ g, support after a certain amount of metal pore volume 50% left and right that generally can descend.CN02133144.8 has provided a kind of silicon-containing alumina carrier and preparation method thereof, this carrier is in aluminium hydroxide or aluminium oxide and deionized water or aqueous solution process, add a kind of nanometer silicon-containing compound of polymolecularity as nano silicon, kneading becomes plastic, then moulding, drying, roasting Kaolinite Preparation of Catalyst carrier, this carrier pore volume is 0.55～0.68mL/g, and average pore diameter is 6.5～9.5nm, and specific area is 270～320m ²/ g, bulk density is 0.58～0.68g/mL, and the pore volume that floods approximately the hydrotreating catalyst (CN02144544.3) after 30% Mo-Ni metal is 0.35～0.38mL/g, and concentrate in aperture is 3～6nm, and specific area is 150～180m ²/ g, in processing, doing is 533 ℃, nitrogen content is 1552ppm, during the decompressed wax oil that sulfur content is 4900ppm (VGO), shows extraordinary hydrogenation activity.Yet, use the standby hydrogenation catalyst of above-mentioned patent system to process when more heavy, decompression deep drawing inferior obtain VGO, the HDN of catalyst, HDS and HDA activity are obviously not high, and can not guarantee long-term operation the service life of catalyst.Therefore, develop more high activity metal content, more large aperture, more the hydrotreating catalyst of large pore volume becomes and solves heavy decompressed wax oil hydrotreatment important channel.

The method that improves hydrotreating catalyst pore volume and specific area is mainly that Main Means has three kinds by improving the pore structure of catalyst carrier, and one adds expanding agent in the catalyst carrier forming process, as sesbania powder and macromolecular organic compound etc.; Its two improvement method for preparing catalyst, for example adopt oil ammonia column to drip ball forming Kaolinite Preparation of Catalyst carrier; It three selects the catalysis material with macroporous structure as carrier component, and is furnished with corresponding preparation method.

Although the interpolation expanding agent has certain effect to the raising of carrier pore volume, as CN98121083.X and CN99113303.X in the preparation process of carrier, add boehmite powder and alumina powder simultaneously, mix the kneadings such as rear and compound expanding agent, become plastic, extruded moulding on banded extruder, then directly large pore volume has been prepared in high-temperature roasting, wide-aperture carrier of hydrogenating catalyst, its pore volume is 0.80～1.30mL/g, can several apertures be 15～20nm, aperture accounts for more than 70% of total pore volume at the pore volume between 10～20nm, but due to the expanding agent added in the catalyst carrier forming process, make the large percentage of mechanical hole in the carrier hole structure, not only actual catalytic reaction effect is helped little, also can the mechanical strength of catalyst be had a certain impact, and its specific area is less, be only 100～200m ²/ g, after carried metal, surface area can be less.Therefore, the macroporous catalyst prepared by this carrier is having certain catalytic effect aspect the HDM of heavy distillate, and is seeming that activity is not high aspect the desulfurization of heavy distillate, denitrogenation.In addition, the pore volume majority that adopts expanding agent to improve is " ink bottle " formula, and the catalytic reaction utilization rate is low.

Can prepare the carrier of high pore volume and specific area although adopt the oil ammonia column forming method, but the mechanical strength of prepared carrier and scuff resistance do not reach the instructions for use of hydrocracking unit, as in document " the reaming research of active aluminum oxide carrier " (petrochemical industry 11 phase Yang Yuwang in 2002 etc.), provided a kind of carrier preparation method who combines above-mentioned two kinds of methods, add the organic matter expanding agent in the carrier preparation process, and adopted the preparation method of oil ammonia column moulding, although the pore volume of carrier is up to 1.4mL/g, crushing strength is only 10N/cm～20N/cm.Usually, more than the crushing strength General Requirements of fixed bed hydrogenation processing catalyst is greater than 100N/cm, can not meet the commercial plant instructions for use that fixed bed hydrogenation is processed catalyst.Simultaneously, the carrier of preparing is when infusion process supported active metal, and specific area and pore volume have again obvious reduction, and the pore volume of final catalyst and specific area improve limited.

The catalysis material that selection has macroporous structure is a kind of method that effectively prepares the macroporous structure carrier of hydrogenating catalyst as carrier component, US6,797, the 153 hydrogenation catalyst pore volumes that adopt large pore material to prepare are 0.5mL/g～1.4mL/g, and specific area is 600m ²/ g～1000m ²/ g, be used in the heavy distillate hydrodesulfurization, the denitrogenation aspect has demonstrated fabulous activity, but the method has adopted the active carbon with macroporous structure, require to use special preparation technology and start-up method, limited its further use on current fixed bed hydrogenation treating apparatus.

Summary of the invention

In order to overcome existing hydrotreating catalyst and preparation method's deficiency, the invention provides that a kind of active metallic content is high, catalyst pore volume and the high hydrotreating catalyst of specific area and preparation method thereof, be suitable for the hydrotreatment process of vacuum distillate more inferior.

Hydrotreating catalyst of the present invention comprises hydrogenation metal component, macroporous aluminium oxide and amorphous aluminum silicide, and specific surface area of catalyst is 150m ²/ g～450m ²/ g, be preferably 220m ²/ g～400m ²/ g; Pore volume is 0.3cm ³/ g～0.7cm ³/ g, be preferably 0.4cm ³/ g～0.6cm ³/ g; Average pore size 10～20nm, preferably 12～20nm.The hydrogenation metal component is at least one in W, Mo, Ni and Co, and the weight content of oxide hydrogenation metal component in catalyst of take is 35%～70%, is preferably 40%～60%.The weight content of amorphous aluminum silicide in catalyst is 10%～60%, and the weight content of macroporous aluminium oxide in catalyst is 5%～50%.

In hydrotreating catalyst of the present invention, macroporous aluminium oxide can be selected the suitable macroporous aluminium oxide product in this area, and preferably pore volume is 1.4mL/g～1.8mL/g, and specific area is 500m ²/ g～550m ²the macroporous aluminium oxide of/g.

In hydrotreating catalyst of the present invention, the amorphous aluminum silicide specific area is 400-650m ²/ g, be preferably 400～550m ²/ g; Pore volume is 1.0～2.0cm ³/ g, be preferably 1.2～1.6cm ³/ g, the silica weight content is 20%～80%, is preferably 30%～65%.Average pore diameter is in 10～20nm scope, preferably at 10～15nm, meleic acid amount (160 ℃ of infrared absorption spectrographic determinations of pyridine) is between 0.3～0.8mmol/g, acid centre is uniformly distributed, amorphous aluminum silicide adopts silica, aluminium oxide to precipitate simultaneously, then uses organic-silicon-modified method preparation.

In hydrotreating catalyst of the present invention, can also contain appropriate binding agent and auxiliary agent, auxiliary agent is generally one or more in phosphorus, boron, fluorine, titanium, zirconium etc.

The preparation method of hydrotreating catalyst of the present invention is as follows: powdery macroporous aluminium oxide precursor is mixed with powdery amorphous aluminum silicide precursor, the pulverulent mixture material is immersed in the solution containing hydrogenation active metals, then filter, drying, through overmolding, activation, prepare final catalyst again.

In hydrotreating catalyst preparation method of the present invention, required auxiliary agent can add in catalyst at arbitrary steps.Catalyst preparation process and condition can adopt method well known to those skilled in the art.

In hydrotreating catalyst preparation method of the present invention, described macroporous aluminium oxide precursor is the macroporous aluminium oxide dry glue powder, and the amorphous aluminum silicide precursor is the contained amorphous silica-alumina dry glue powder.The dry glue of macroporous aluminium oxide can adopt existing method preparation, as described in CN200510047483.1.

In hydrotreating catalyst preparation method of the present invention, described contained amorphous silica-alumina dry glue powder adopts following method preparation:

(1) acid aluminium salt solution is (as AlCl ₃, Al (NO ₃) ₃, Al ₂(SO ₄) ₃one or more in solution) with during the mixed solution of the alkaline sodium silicate of preparing in proportion and sodium aluminate carries out with plastic, react, reaction temperature is controlled at 20～80 ℃, and the pH value is in 4.0～9.5 scopes.

(2) add the organosilicon source after plastic, the silicon source can comprise one or more in organic silicone oil or estersil class etc., organosilyl addition is pressed 5%～40% of the required total silicon amount of final products, be preferably 10%～30%, adjustment pH value and temperature are carried out aging temperature and are controlled at 60～80 ℃, the pH value is in 6.0～10.0 scopes, and ageing time is 60～300min.

(3) (2) gained colloidal sol is filtered, washed.

(4) (3) gained filter cake is carried out to drying, pulverizing, make the contained amorphous silica-alumina dry glue powder.

In hydrotreating catalyst preparation method of the present invention, hydrogenation active metals is generally group vib and VIII family metallic salt, as the salt of the metals such as W, Mo, Ni, Co one or more, can add as required the required various auxiliary agents of catalyst in dipping solution.Dipping process generally can adopt excessive impregnation method, and the dipping solution amount is more than the saturated pick up of carrier material, and general solid-liquid volume ratio is 1: 5～1: 20, is beneficial to abundant dipping.In dipping solution, the concentration of the slaines such as W, Mo, Ni, Co is determined according to catalyst activity metal requirement, as metal salt concentrations in dipping solution is generally 10～150g/100mL by oxide.Filtration after dipping and dry this area commonsense method and the condition of adopting.Can add as required one or more in peptization acid, adhesive component, expanding agent, extrusion aid etc. in the shaping of catalyst process, so that moulding smoothly.Activation after moulding adopts first dry roasting process, obtains final catalyst prod, and roasting is generally 300～600 ℃ of lower roastings 1～10 hour, and drying adopts this area usual terms.

Hydrotreating catalyst of the present invention is by preparing the raw material of large pore volume, bigger serface, and adopt suitable preparation method, can guarantee that catalyst is when having higher hydrogenation tenor alive, there is larger pore volume and specific area, be suitable for the hydrotreatment process of heavier vacuum distillate more inferior.

Catalyst of the present invention not only has the pore structure of super large, quite high crushing strength and scuff resistance have also been guaranteed simultaneously, and can be according to actual needs, regulate the acid strength of carrier in wide region, can meet the instructions for use that hydrotreating catalyst supports hydrogenation metal and commercial plant, so the present invention has very high practicality.

Hydrotreating catalyst preparation process of the present invention adopts carrier material powder dipping method, with carrier impregnation after conventional moulding, compares, and the powder dipping can absorb more maceration extract, pick up than moulding after the carrier pick up improve several times.Therefore maceration extract does not need higher metal concentration just can prepare the final catalyst prod that active metallic content is higher.Due to the dipping solution that does not need high concentration, solution preparation is simple, and stable in properties is applicable to commercial scale and uses.Rarer slaine maceration extract can reduce the viscosity of solution, reduces solution surface tension, can weaken like this impact of capillary resistance phenomenon in dipping process.Not only can guarantee that in catalyst, metal component has higher content, can also further improve the decentralization of metal at carrier surface.

Catalyst carrier material is after hydrothermal treatment consists, and pore passage structure is more stable, at follow-up dipping, roll, still can keep pore passage structure preferably in moulding, calcination process process, has larger pore volume and specific area.Support acidity after hydrothermal treatment consists weakens greatly, and residue is acid take weak acid as main, is conducive to improve the Hydrogenation of catalyst.In addition, after the carrier material dipping reactive metal solution of hydrothermal treatment consists, be easy to and excessive residue dipping solution isolated by filtration.

The present invention adopts the modified macroporous aluminium oxide of extraordinary silicon as carrier, and this patented product has pore volume and the specific area of super large, can support more metal component, and can guarantee that metal component can be good at disperseing on carrier.The inventive method can adopt single macropore alumina supporter, can not only guarantee that catalyst has the uniformity of higher tenor and better metal component distribution, can also guarantee that catalyst has larger pore volume and surface area.

The amorphous aluminum silicide used in catalyst carrier of the present invention adopts sial coprecipitation mode preparation simultaneously, introduce the organosilicon source as the modification expanding agent after cemented into bundles, so not only can obtain the uniform amorphous aluminum silicide of Distribution of silicon and aluminium, can also improve the silica alumina ratio of amorphous aluminum silicide, increase amorphous aluminum silicide pore volume and specific area, can prepare the amorphous aluminum silicide of the macropore that meets the catalyst performance needs, bigger serface, high silica alumina ratio.Due to being uniformly distributed of aluminium oxide and silica, make the acid centre of amorphous aluminum silicide also can be uniformly distributed.After introducing organosilicon in the preparation process of amorphous aluminum silicide, in dry and roasting process, organic matter expands and volatilizees, and makes amorphous aluminum silicide obtain larger pore volume and specific area, and can adjust pore volume and the specific area that organosilyl addition is adjusted product according to actual operation requirements.In unbodied sial preparation process, do not use the pollutants such as ammoniacal liquor, there is no the ammonia nitrogen discharge.The silicon source adopts cheap waterglass and a small amount of organosilicon source to combine, and makes preparation cost be controlled effectively.Therefore the method has the characteristics such as preparation technology is simple, cost is low, pollution-free, and applicable commercial scale is promoted the use of.Amorphous aluminum silicide can be by adjusting the ratio of alkaline solution mesosilicic acid sodium and sodium aluminate in preparation process, and adjustment sodium metasilicate and organosilyl ratio, control flexibly the silica alumina ratio of amorphous aluminum silicide product, can obtain the amorphous aluminum silicide of dioxide-containing silica at 20%～80% relative broad range, in amorphous aluminum silicide, the content of silica has direct relation with acidity again, therefore can further carry out its acidity of modulation, come for different instructions for uses, preparation has different acid amorphous silicon aluminums.

In the preparation process of hydrotreating catalyst of the present invention, maceration extract can recycle.Therefore the method has that preparation technology is simple, cost is low, pollute the characteristics such as little, and applicable commercial scale is promoted the use of.

The specific embodiment

A kind of concrete preparation process of amorphous aluminum silicide in catalyst of the present invention is as follows:

(1) preparation of acid solution, with AlCl ₃solution be prepared as example: general aluminium oxide is reacted under 90～120 ℃ with hydrochloric acid, is used the active carbon deferrization, made Fe/Al by weight ₂o ₃value is less than 0.005%, makes smart AlCl ₃solution, then diluted, concentration is 10～60g Al ₂o ₃working solution when/L can be used as plastic.

(2) preparation of alkaline solution, first make NaAlO ₂solution adds sodium silicate solution under stirring condition, prepares transparent mixed solution, in mixed solution with Al ₂o ₃meter is containing 5～80g Al ₂o ₃/ L, with SiO ₂meter is containing 5～120g SiO ₂/ L.

(3) plastic process: acid solution and alkaline solution are joined in plastic cans with certain flow velocity simultaneously, and stirred, gelation time control is at 60～100min, the plastic reaction temperature is controlled at 20～80 ℃, preferably be controlled at 50～70 ℃, the pH value of plastic course of reaction is controlled in 4.0～9.5 scopes.Add organic silicon solvent after plastic reaction, then slurries are carried out agingly, aging pH value is 6.0～10.0, and temperature is controlled at 60～80 ℃, and ageing time is 60～300min.

(4) filter, wash: aging slurries are filtered, mother liquor is separated, the filter cake obtained is washed by deionized water, and washing pulp time control temperature processed is between 60～80 ℃, and wash time is 20～50min, and washing times is 3～5 times.

(5) drying: the filter cake of (4) gained is carried out to drying 1～20 hour under 100～150 ℃.

In hydrotreating catalyst preparation process of the present invention, the preparation of active hydrogenation component solution can be by this area conventional method.Take tungsten and nickel as example, the dipping solution preparation: get a certain amount of deionized water under stirring, add gradually nickel nitrate and ammonium metatungstate crystal, after all dissolving, static, filter, obtain metal impregnation solution, wherein WO ₃content 20.0～50.0gWO ₃/ 100mL, NiO content 2.0～15.0gNiO/100mL.The preparation of various metal impregnation solution belongs to this area mature technology.Solid-liquid volume ratio during dipping solution and carrier material dipping is generally 1: 5～and 1: 20, dip time is generally 30～120min.Then carry out suction filtration, the filter cake butt is controlled at 15%～30%, and under 100～150 ℃ of conditions, drying is 2～6 hours, and containing metal powder butt is 60%～90%, is then pulverized granularity control 100～200 orders.

Hydrogenation catalyst of the present invention most preferably adopts the mode moulding of extrusion, generally can adopt cylindrical, clover, bunge bedstraw herb or other abnormal shape, then carries out drying, and roasting, prepare hydrotreating catalyst.Drying generally under 50～200 ℃ dry 2～20 hours, roasting is generally 350～550 ℃ of roastings 1～10 hour.

In the present invention, specific surface and pore volume adopt the low temperature liquid nitrogen physisorphtion, and meleic acid amount, B acid and L acid adopt the pyridine adsorption infra-red sepectrometry, and wherein the summation of B acid and L acid is the meleic acid amount, and trace element adopts plasma emission spectrometry.

The following examples are for illustrating in greater detail the preparation method of carrier of the present invention, but scope of the present invention is not only limited to the scope of these embodiment, and the percentage composition related to is weight percentage.

Example 1

Adopt patent CN02144544.3 example (1) and (2) method preparation contrast hydrotreating catalyst numbering CatA and CatB.

Example 2 (contrast scheme)

(Tianjin is cut Noya Inc. and is produced, pore volume 0.80mL/g, specific area 295m to get the 580g macroporous aluminium oxide ²/ g, butt 72.1%), the little porous aluminum oxide of 386g (Germany produces the SB powder) prepares adhesive (butt 26.2%), add 6g sesbania powder, roll 30 minutes, add appropriate distilled water, make mixture become can squeeze the paste shape, extrusion, banded extruder orifice plate diameter is 1.5mm clover.Wet bar under 120 ℃ dry 4 hours, then carry out roasting, 550 ℃ of temperature, 3 hours time, numbering HT-1S.Get HT-1S carrier (MoO in the molybdenum nickel solution ₃content 40.7g/100mL, NiO content 6.5g/100mL) carry out the supersaturation dipping, the dipping rear catalyst, 480 ℃ of roastings 3 hours, is prepared the catalyst finished product and is numbered HT-1.

Example 3 (contrast scheme)

Get the 880g macroporous aluminium oxide, add the rare nitric acid of 4g/100mL to be rolled into the paste shape, extrusion, banded extruder orifice plate diameter is 1.5mm clover.Wet bar under 120 ℃ dry 4 hours, then carry out roasting, 550 ℃ of temperature, 3 hours time, numbering HT-2S.Get HT-2S carrier (MoO in the molybdenum nickel solution ₃content 38.8g/100mL, NiO content 5.6g/100mL) carry out the supersaturation dipping, the dipping rear catalyst, 480 ℃ of roastings 3 hours, floods active component one time by the same way again.Prepare the catalyst finished product and be numbered HT-2.

Example 4 (the present invention program)

Get super big hole modified aluminas dry glue 556g (pore volume 1.70mL/g, specific area 520m prepared by CN200510047483.1 ²/ g, butt 75.1%), 100g contained amorphous silica-alumina dry glue (pore volume 1.40mL/g, specific area 550m ²/ g, butt 74.3%, average pore diameter is 13.6nm), mix, add solution impregnation containing Mo, Ni salt (catalyst such as reactive metal addition form press table 1 catalyst form design and determine), then filter, dry, pulverizing.Add the appropriate binding agent by the aperture alumina preparation, add 6g sesbania powder, roll 30 minutes, add appropriate distilled water, make mixture become can squeeze the paste shape, extrusion, banded extruder orifice plate diameter is 1.5mm clover.Wet bar under 120 ℃ dry 4 hours, then carry out roasting, and 550 ℃ of temperature, 3 hours time, prepare the catalyst finished product and be numbered HT-3.

The amorphous aluminum silicide preparation process is as follows: 2000mL is contained to Al ₂o ₃the AlCl of 5g/100mL ₃solution with containing Al ₂o ₃5g/100mL and SiO ₂the sodium aluminate of 15g/100mL and sodium metasilicate mixed solution drip are added in the plastic reaction filling that temperature is 65 ℃ of stirrings, and keeping the pH value is 8.0, and reaction contact time 40min., with AlCl ₃solution drips off and is as the criterion.Continue to stir 10min, drip containing SiO ₂10g/100mL organic silicone oil (trade mark 5001) 350mL, time for adding is 20min.Then use 5% sodium hydroxide solution by slurry pH value be adjusted into 9.0 carry out aging.Ageing time is 1.5 hours.Product is filtered to the deionized water that is then 1: 20 by solid-to-liquid ratio washing, 70 ℃ of wash temperatures, washing times 3 times.To gained filter cake dry 3h under 120 ℃.

Example 5 (the present invention program)

Press the described method of embodiment 4 (the catalyst composition is pressed table 1 design and determined), amorphous aluminum silicide wherein (pore volume 1.32mL/g, specific area 485m ²/ g, butt 75.4%, average pore diameter is 12.7nm) and adopt following method preparation: 6000mL is contained to Al ₂o ₃the AlCl of 5g/100mL ₃solution with containing Al ₂o ₃5g/100mL and SiO ₂the sodium aluminate of 15g/100mL and sodium metasilicate mixed solution drip are added in the plastic reaction filling that temperature is 65 ℃ of stirrings, and keeping the pH value is 8.0, and reaction contact time 40min., with AlCl ₃solution drips off and is as the criterion.Continue to stir 10min, drip ethyl orthosilicate 120mL, time for adding is 20min.Then use 5% sodium hydroxide solution by slurry pH value be adjusted into 9.0 carry out aging.Ageing time is 1.5 hours.Product is filtered to the deionized water that is then 1: 20 by solid-to-liquid ratio washing, 70 ℃ of wash temperatures, washing times 3 times.To gained filter cake dry 3h under 120 ℃.

Prepare the catalyst finished product and be numbered HT-4.

Example 6 (the present invention program)

According to the described method of embodiment 5 (the catalyst composition is pressed table 1 design and determined), prepare the catalyst finished product and be numbered HT-5.

Example 7 (the present invention program)

According to the described method of embodiment 5 (the catalyst composition is pressed table 1 design and determined), prepare the catalyst finished product and be numbered HT-6.

Example 8 (the present invention program)

Press example 4 methods, add respectively the auxiliary agents such as a certain amount of ammonium fluoride, phosphoric acid, zirconia (the catalyst composition is pressed table 1 design and determined) in forming process, prepare the catalyst finished product and be numbered respectively HT-F, HT-P and HT-Zr.

In the present embodiment, above each routine catalyst is carried out to instrumental analysis and activity rating.Each routine catalyst physico-chemical property is shown in Table 1, and catalyst forms take weight as benchmark.

Table 1 catalyst physico-chemical property

Table 1 (continuing) catalyst physico-chemical property

Evaluating apparatus carries out on the 200mL small hydrogenation device, before activity rating, catalyst is carried out to presulfurization.The raw materials used grease separation of evaluation of catalyst activity is done feedstock oil with a kind of height of the deep drawing of reducing pressure, and character and reaction process condition are in Table 2 and table 3, and catalyst denitrogenation relative activity comparing result is in Table 4.

Table 2. feedstock oil character

Table 3. evaluating catalyst process conditions

Table 4. catalyst denitrogenation relative activity comparing result

Claims (9)

1. a hydrotreating catalyst, comprise hydrogenation metal component, macroporous aluminium oxide and amorphous aluminum silicide, it is characterized in that: specific surface area of catalyst is 150m ²/ g～450m ²/ g, pore volume is 0.3cm ³/ g～0.7cm ³/ g, average pore size 10～20nm, the hydrogenation metal component is at least one in W, Mo, Ni and Co, the weight content of oxide hydrogenation metal component in catalyst of take is 40%～70%; The amorphous aluminum silicide specific area is 400-650m ²/ g, pore volume is 1.0～2.0cm ³/ g, the silica weight content is 20%～80%, average pore diameter is in 10～20nm scope;

The preparation method of catalyst is as follows: powdery macroporous aluminium oxide precursor is mixed with powdery amorphous aluminum silicide precursor, the pulverulent mixture material is immersed in the solution containing hydrogenation active metals, then filter, drying, again through overmolding, activation, prepare final catalyst, described macroporous aluminium oxide precursor is the macroporous aluminium oxide dry glue powder, and the amorphous aluminum silicide precursor is the contained amorphous silica-alumina dry glue powder.

2. according to catalyst claimed in claim 1, it is characterized in that: the weight content of amorphous aluminum silicide in catalyst is 10%～60%, and the weight content of macroporous aluminium oxide in catalyst is 5%～50%.

3. according to the described catalyst of claim 1 or 2, it is characterized in that: specific surface area of catalyst is 220m ²/ g～400m ²/ g, pore volume is 0.4cm ³/ g～0.6cm ³/ g, average pore size 12～20nm, the weight content of oxide hydrogenation metal component in catalyst of take is 40%～60%.

4. according to the described catalyst of claim 1 or 2, it is characterized in that: the macroporous aluminium oxide pore volume is 1.4mL/g～1.8mL/g, and specific area is 500m ²/ g～550m ²/ g.

5. according to the described catalyst of claim 1 or 2, it is characterized in that: the amorphous aluminum silicide specific area is 400～550m ²/ g, pore volume is 1.2～1.6cm ³/ g, the silica weight content is 30%～65%, average pore diameter is in 10～15nm scope.

6. according to catalyst claimed in claim 1, it is characterized in that: in hydrotreating catalyst, also contain binding agent and auxiliary agent, auxiliary agent is one or more in phosphorus, boron, fluorine, titanium, zirconium.

7. the preparation method of the arbitrary catalyst of claim 1 to 6, powdery macroporous aluminium oxide precursor is mixed with powdery amorphous aluminum silicide precursor, the pulverulent mixture material is immersed in the solution containing hydrogenation active metals, then filter, drying, again through overmolding, activation, prepare final catalyst, described macroporous aluminium oxide precursor is the macroporous aluminium oxide dry glue powder, and the amorphous aluminum silicide precursor is the contained amorphous silica-alumina dry glue powder.

8. in accordance with the method for claim 7, it is characterized in that described contained amorphous silica-alumina dry glue powder adopts following method preparation:

(1) during the alkaline sodium silicate of acid aluminium salt solution and preparation in proportion and the mixed solution of sodium aluminate carry out and plastic react, reaction temperature is controlled at 20～80 ℃, the pH value is in 4.0～9.5 scopes;

(2) add the organosilicon source after plastic, the silicon source is one or more in organic silicone oil or estersil class, organosilyl addition is pressed 5%～40% of the required total silicon amount of final products, adjusting pH value and temperature carries out aging, aging temperature is controlled at 60～80 ℃, the pH value is in 6.0～10.0 scopes, and ageing time is 60～300min;

(3) (2) gained colloidal sol is filtered, washed;

(4) (3) gained filter cake is carried out to drying, pulverizing, make the contained amorphous silica-alumina dry glue powder.

9. in accordance with the method for claim 8, it is characterized in that: in the mixed solution of alkaline sodium silicate and sodium aluminate, with Al ₂o ₃meter is containing 5～80g Al ₂o ₃/ L, with SiO ₂meter is containing 5～120g SiO ₂/ L.